TY - JOUR
T1 - Plasticized Cellulosic Films by Partial Esterification and Welding in Low-Concentration Ionic Liquid Electrolyte
AU - Niu, Xun
AU - Liu, Yating
AU - King, Alistair W.T.
AU - Hietala, Sami
AU - Pan, Hui
AU - Rojas, Orlando J.
N1 - Funding Information:
H.P., X.N., and Y.L. are grateful for the financial support by the Forestry Industry Research Special Funds for Public Welfare Projects (201504602), Nature Science Foundation of China (31770631), and the Priority Academic Program Development (PAPD) project of Jiangsu Higher Education Institutions. O.J.R. and X.N. acknowledge funding support by European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (ERC Advanced Grant agreement No. 788489, “BioElCell”). A.W.T.K. acknowledges funding support from the Finnish Academy under the project “WTF-Click-Nano” (311255).
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/5/13
Y1 - 2019/5/13
N2 - Alternatives to petroleum-based plastics are of great significance not only from the point of view of their scientific and practical impact but to reduce the environmental footprint. Inspired by the composition and structure of wood's cell walls, we used phenolic acids to endow cellulosic fibers with new properties. The fiber dissolution and homogeneous modification were performed with a recyclable ionic liquid (IL) (tetrabutylammonium acetate ([N4444][OAc]):dimethyl sulfoxide) to attain different levels of reaction activity for three phenolic acids (p-hydroxybenzoic acid, vanillic acid, and syringic acid). The successful autocatalytic Fischer esterification reaction was thoroughly investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, elemental analysis, and nuclear magnetic resonance spectroscopy (13C CP-MAS, diffusion-edited 1H NMR and multiplicity-edited heteronuclear single quantum coherence). Control of the properties of cellulose in the dispersed state, welding, and IL plasticization were achieved during casting and recrystallization to the cellulose II crystalline allomorph. Films of cellulose carrying grafted acids were characterized with respect to properties relevant to packaging materials. Most notably, despite the low degree of esterification (DS < 0.25), the films displayed a remarkable strength (3.5 GPa), flexibility (strains up to 35%), optical transparency (>90%), and water resistance (WCA ∼90°). Moreover, the measured water vapor barrier was found to be similar to that of poly(lactic acid) composite films. Overall, the results contribute to the development of the next-generation green, renewable, and biodegradable films for packaging applications.
AB - Alternatives to petroleum-based plastics are of great significance not only from the point of view of their scientific and practical impact but to reduce the environmental footprint. Inspired by the composition and structure of wood's cell walls, we used phenolic acids to endow cellulosic fibers with new properties. The fiber dissolution and homogeneous modification were performed with a recyclable ionic liquid (IL) (tetrabutylammonium acetate ([N4444][OAc]):dimethyl sulfoxide) to attain different levels of reaction activity for three phenolic acids (p-hydroxybenzoic acid, vanillic acid, and syringic acid). The successful autocatalytic Fischer esterification reaction was thoroughly investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, elemental analysis, and nuclear magnetic resonance spectroscopy (13C CP-MAS, diffusion-edited 1H NMR and multiplicity-edited heteronuclear single quantum coherence). Control of the properties of cellulose in the dispersed state, welding, and IL plasticization were achieved during casting and recrystallization to the cellulose II crystalline allomorph. Films of cellulose carrying grafted acids were characterized with respect to properties relevant to packaging materials. Most notably, despite the low degree of esterification (DS < 0.25), the films displayed a remarkable strength (3.5 GPa), flexibility (strains up to 35%), optical transparency (>90%), and water resistance (WCA ∼90°). Moreover, the measured water vapor barrier was found to be similar to that of poly(lactic acid) composite films. Overall, the results contribute to the development of the next-generation green, renewable, and biodegradable films for packaging applications.
KW - Biodegradable Plastics/chemical synthesis
KW - Cellulose/analogs & derivatives
KW - Esterification
KW - Ionic Liquids/chemistry
KW - Phenols/chemistry
KW - Product Packaging/methods
KW - Tensile Strength
UR - http://www.scopus.com/inward/record.url?scp=85065676159&partnerID=8YFLogxK
U2 - 10.1021/acs.biomac.9b00325
DO - 10.1021/acs.biomac.9b00325
M3 - Article
C2 - 30983326
AN - SCOPUS:85065676159
SN - 1525-7797
VL - 20
SP - 2105
EP - 2114
JO - Biomacromolecules
JF - Biomacromolecules
IS - 5
ER -